Compound with indolocarbazole moieties and devices containing such compound

ABSTRACT

A compound composed of a plurality of optionally substituted indolocarbazole moieties which are the same or different from each other.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part application of co-pendingU.S. application Ser. No. 11/011,678 (filing date Dec. 14, 2004) fromwhich priority is claimed, the disclosure of which is totallyincorporated herein by reference.

Yiliang Wu et al., U.S. application Ser. No. ______ (Attorney Docket No.A3389-US-CIP), filed on ______, titled “THIN FILM TRANSISTORS INCLUDINGINDOLOCARBAZOLES” is a continuation-in-part application of co-pendingU.S. application Ser. No. 11/011,441 (filing date Dec. 14, 2004) fromwhich priority is claimed, the disclosure of which is totallyincorporated herein by reference.

Yuning Li et al., U.S. application Ser. No. 11/011,901 (Attorney DocketNo. 20031573-US-NP), filed on Dec. 14, 2004, titled “PROCESS TO FORMCOMPOUND WITH INDOLOCARBAZOLE MOIETIES.”

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

This invention was made with United States Government support underCooperative Agreement No. 70NANBOH3033 awarded by the National Instituteof Standards and Technology (NIST). The United States Government hascertain rights in the invention.

BACKGROUND OF THE INVENTION

Organic electronics has been an intense research topic over the last twodecades or so because of their enormous commercial potential. Someillustrative organic electronic devices are organic light-emittingdiodes, organic thin film transistors, and organic photovoltaics. One ofthe key components in these devices is organic semiconductors which havereceived extensive research and development efforts. In the field oforganic electronics, organic thin-film transistors (OTFTs) have inrecent years attracted great attention as a low-cost alternative tomainstream amorphous silicon-based transistors for electronicapplications. OTFTs are particularly suited for applications wherelarge-area circuits (e.g., backplane electronics for large displays),desirable form factors and structural features (e.g., flexibility fore-paper), and affordability (e.g., ultra low cost for ubiquitous radiofrequency identification tags) are essential.

Organic semiconductors are typically based on: (1) acenes such astetracene, pentacene and their derivatives, (2) thiophenes such asoligothiophenes and polythiophenes, (3) fused-ring thiophene-aromaticsand thiophene-vinylene/arylene derivatives. Most of these semiconductorsare either insoluble in common organic solvents or sensitive to air, andare therefore not suitable for fabricating low-cost OTFTs via liquidpatterning and deposition processes under ambient conditions. There istherefore a critical need addressed by embodiments of the presentinvention to develop liquid-processable and air stable organicsemiconductor compounds to enable low-cost OTFTs. The present inventionin embodiments also provides a facile process for the preparation ofthese organic semiconductors which meet the fabrication requirements forlow-cost OTFTs.

The following documents provide background information:

Christos D. Dimitrakopoulos et al., “Organic Thin Film Transistors forLarge Area Electronics,” Adv. Mater., Vol. 14, No. 2, pp. 99-117 (2002).

Salem Wakim et al., “Organic Microelectronics: Design, Synthesis, andCharacterization of 6,12-Dimethylindolo[3,2-b]Carbazoles,” Chem. Mater.Vol. 16, No. 23, pp. 4386-4388 (published on web Jul. 7, 2004).

Nan-Xing Hu et al.,“5-11-Dihydro-5,11-di-1-naphthylindolo[3,2-b]carbazole: Atropisomerismin a Novel Hole-Transport Molecule for Organic Light-Emitting Diodes,”J. Am. Chem. Soc., Vol. 121, pp. 5097-5098 (1999).

Hu et al., U.S. Pat. No. 5,942,340.

Hu et al., U.S. Pat. No. 5,952,115.

Hu et al., U.S. Pat. No. 5,843,607.

SUMMARY OF THE DISCLOSURE

The present invention is accomplished in embodiments by providing acompound comprising a plurality of optionally substitutedindolocarbazole moieties which are the same or different from eachother.

In other embodiments, there is provided a compound comprising aplurality of optionally substituted indolocarbazole moieties, which arethe same or different from each other, wherein the indolocarbazolemoieties are independently selected from the structures (A), (B), (C),(D), (E), (F) and (G), or a mixture thereof:

wherein for each of the structures (A) through (G), each R isindependently selected from a group consisting of a hydrogen, ahydrocarbon group and a heteroatom-containing group, wherein each of thestructures (A) through (G) is optionally peripherally substituted.

There is further provided in embodiments an electronic devicecomprising:

a substrate;

an electrically conductive layer or a dielectric layer, or both theelectrically conductive layer and the dielectric layer; and

a semiconductor layer comprising a compound comprising a plurality ofoptionally substituted indolocarbazole moieties which are the same ordifferent from each other.

There is also provided in embodiments a thin film transistor comprising:

(a) a gate dielectric layer;

(b) a gate electrode;

(c) a semiconductor layer;

(d) a source electrode; and

(e) a drain electrode,

wherein the gate dielectric layer, the gate electrode, the semiconductorlayer, the source electrode, and the drain electrode are in any sequenceas long as the gate electrode and the semiconductor layer both contactthe gate dielectric layer, and the source electrode and the drainelectrode both contact the semiconductor layer, andwherein the semiconductor layer includes a compound comprising aplurality of optionally substituted indolocarbazole moieties, which arethe same or different from each other, wherein the indolocarbazolemoieties are independently selected from the structures (A), (B), (C),(D), (E), (F) and (G), or a mixture thereof:

wherein for each of the structures (A) through (G), each R isindependently selected from a group consisting of a hydrogen, ahydrocarbon group and a heteroatom-containing group, wherein each of thestructures (A) through (G) is optionally peripherally substituted.

In additional embodiments, there is provided a process comprising:

reacting a reaction mixture comprised of one or more optionallysubstituted indolocarbazoles, a reaction medium, and a coupling agent ata reaction temperature to form a compound comprising a plurality ofoptionally substituted indolocarbazole moieties which are the same ordifferent from each other.

In further embodiments, there is provided a process comprising:

reacting a reaction mixture comprised of one or more optionallysubstituted indolocarbazoles, a reaction medium, and a coupling agent ata reaction temperature to form a compound comprising a plurality ofoptionally substituted indolocarbazole moieties which are the same ordifferent from each other, wherein the one or more optionallysubstituted indolocarbazoles are independently selected from the groupconsisting of structures (A), (B), (C), (D) (E), (F) and (G), or amixture thereof:

wherein for each of the structures (A) through (G), each R isindependently selected from a group consisting of a hydrogen, ahydrocarbon group and a heteroatom-containing group, wherein each of thestructures (A) through (G) is optionally peripherally substituted.

BRIEF DESCRIPTION OF THE DRAWINGS

Other aspects of the present invention will become apparent as thefollowing description proceeds and upon reference to the followingfigures which represent exemplary embodiments:

FIG. 1 represents a first embodiment of the present invention in theform of an OTFT;

FIG. 2 represents a second embodiment of the present invention in theform of an OTFT;

FIG. 3 represents a third embodiment of the present invention in theform of an OTFT; and

FIG. 4 represents a fourth embodiment of the present invention in theform of an OTFT.

Unless otherwise noted, the same reference numeral in different Figuresrefers to the same or similar feature.

DETAILED DESCRIPTION

The present compound (“Compound”) is composed of a plurality ofoptionally substituted indolocarbazole moieties which are the same ordifferent from each other wherein the Compound is synthesized from oneor more optionally substituted indolocarbazoles. The terms“indolocarbazole moieties” and “indolocarbazole” refer to a structurecomposed of one carbazole moiety (optionally substituted) and one, twoor more indolo moieties (each optionally substituted), wherein thecarbazole moiety is fused with one or more of the indolo moieties, andany adjacent indolo moieties are fused together. The fusing of thecarbazole moiety with the one or more indolo moieties, and the fusing ofany adjacent indolo moieties can occur at any available positions. Thecarbazole moiety may be positioned at any suitable position in thestructure such as at the end or the middle of the structure.

In embodiments, the Compound is a polymer, an oligomer, or a molecularcompound. The polymer has a weight average molecular weight (M_(w)) offor example from about 5000 to about 1,000,000, and number averagemolecular weight (M_(N)) of for example from about 4000 to about 200,000relative polystyrene standards as measured by gel permeationchromatography. The polymer could be a homopolymer, copolymer, orterpolymer, and the like. The oligomer refers to a mixture of lowmolecular weight Compounds which comprises a small number of repeatingunits of one or more chemical entities, and is therefore a subset of apolymer. The oligomer has a M_(w) of for example less than 5000, and aM_(N) of for example less than 4000. The molecular compound has awell-defined chemical structure with an exact molecular weight. It isunderstood that trace amounts of impurity may be present in themolecular compound. The molecular compound has a purity of, for exampleat least about 90% by weight, at least about 95% by weight, or at leastabout 99% by weight.

The Compound (a single Compound or a mixture of two or more differentCompounds) may be used for any suitable applications, particularly as asemiconductor for electronic devices. The phrase “electronic devices”refers to macro-, micro- and/or nano-electronic devices such as thinfilm transistors, organic light emitting diodes, RFID tags,photovoltaic, and other electronic devices.

In embodiments, the Compound is unsubstituted or substituted with one ormore substituents in any suitable substitution pattern. For substitutedembodiments of the Compound, the substitution can be for example thefollowing: (1) one or more nitrogen substitutions with no peripheralsubstitution; (2) one or more peripheral substitutions with no nitrogensubstitution; or (3) one or more nitrogen substitutions and one or moreperipheral substitutions. In embodiments, all the nitrogen atoms of theCompound are substituted with the same or different substituents, withthe Compound being optionally peripherally substituted. In embodiments,the Compound is nitrogen substituted (and optionally peripherallysubstituted) wherein the one or more nitrogen substituents areindependently selected from the group consisting of a hydrocarbon groupand a heteroatom-containing group, or a mixture thereof. In embodiments,the Compound is peripherally substituted (and optionally nitrogensubstituted) wherein the one or more peripheral substituents areindependently selected from the group consisting of a hydrocarbon group,a heteroatom-containing group, and a halogen, or a mixture thereof.

The phrases “peripherally substituted” and “peripheral substitution”refer to at least one substitution (by the same or differentsubstituents) on any one or more aromatic rings of the Compoundregardless whether the aromatic ring is a terminal aromatic ring or aninternal aromatic ring (that is, other than at a terminal position).

In embodiments, the indolocarbazole moieties of the Compound areindependently selected from the group consisting of structures (A), (B),(C), (D), (E), (F), and (G), or a mixture thereof.

wherein for each of the structures (A) through (G), each R isindependently selected from a group consisting of a hydrogen, ahydrocarbon group and a heteroatom-containing group (that is, eachnitrogen atom can have the same or different R), wherein each of thestructures (A) through (G) is optionally peripherally substituted by oneor more substituents selected from the group consisting of a hydrocarbongroup, a heteroatom-containing group, and a halogen, or a mixturethereof.

It is noted that structures (A) through (G) are discussed in twocontexts. In the context of the optionally substituted indolocarbazolemoieties, structures (A) through (G) are moieties depicted without thecovalent bonding which connects adjacent indolocarbazole moieties but itis understood that in the Compound adjacent indolocarbazole moieties ofstructures (A) through (G) are covalent bonded. In the context ofoptionally substituted indolocarbazoles useful in the synthesis of theCompound, structures (A) through (G) are exemplary indolocarbazoles.

The optionally substituted indolocarbazoles moieties are covalent bondedat any suitable position to form the Compound. As an illustration forstructure (A), the covalent bonding can occur at 2 and 8 positions or 3and 9 positions depending on reactions and reaction conditions. Forexample, using indolocarbazole of structure (A) as the startingmaterials, treatment with FeCl₃ can lead to covalent bonding at the 2and 8 positions of structure (A). On the other hand, if3,9-dibromoindolocarbazole is used as the starting material and treatedwith Zn in the presence of NiCl₂/2,2′-dipyridil, then covalent bondingwill occur at the 3 and 9 positions of structure (A).

The hydrocarbon group for the optionally substituted indolocarbazolemoieties contains for example from 1 to about 50 carbon atoms, or from 1to about 30 carbon atoms, and may be for example a straight chain alkylgroup, a branched alkyl group, a cyclic aliphatic group, an aryl group,an alkylaryl group, and an arylalkyl group. Exemplary hydrocarbon groupsinclude for example methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl,octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl,cyclopentyl, cyclohexyl, cycloheptyl, and isomers thereof.

The heteroatom-containing group for the optionally substitutedindolocarbazole moieties has for example 2 to about 200 atoms, or from 2to about 100 atoms) and may be for example a nitrogen-containing group,an alkoxy group, a heterocyclic system, an alkoxyaryl, an arylalkoxy,and a halogenated hydrocarbon (where the halogen is for examplefluorine, bromine, chlorine, or iodine, or a mixture thereof). Exemplaryheteroatom-containing groups include for example fluoroalkyl,fluoroaryl, cyano, nitro, carbonyl, carboxylate, amino (optionallysubstituted with one or two substituents such as for example ahydrocarbon group described herein), and alkoxy (having for example 1 toabout 18 carbon atoms). In embodiments, the heteroatom-containing groupis independently selected from the group consisting of fluoroalkyl(having for example 1 to about 18 carbon atoms), fluoroaryl, cyano,nitro, carbonyl, carboxylate, alkoxy (having for example 1 to about 18carbon atoms), and amino (optionally substituted with one or twosubstituents such as for example a hydrocarbon group described herein),or a mixture thereof. In embodiments, the heteroatom-containing group isan optionally substituted carbazole group.

In embodiments, the heteroatom-containing group is an optionallysubstituted thienyl comprising one, two, or more thienyl units, eachthienyl unit being the same or different from each other and ofexemplary structure (A)

where R₁ is independently selected from a hydrocarbon group (such asthose described herein for the optionally substituted indolocarbazolemoieties), a heteroatom containing group (such as those described hereinfor the optionally substituted indolocarbazole moieties), and a halogen(such as those described herein for the optionally substitutedindolocarbazole moieties), and where m is 0, 1, 2 or 3.

In embodiments, R₁ is part of a cyclic ring structure fused to thethienyl unit, where the fused cyclic ring structure is of any size suchas for example a 4 to 8 membered ring, particularly, a 5 or 6 memberedring, wherein R₁ is attached at the carbon atoms at for example thethird ring position and the fourth ring position of the thienyl unit, orany other available ring positions. The fused ring structure (containingR₁) may be either a hydrocarbon group described herein or a heteroatomcontaining group described herein. Where R₁ is part of a ring structurefused to a thienyl unit, m is 1 even though R₁ in this situation isbonded to two positions of the thienyl unit. Examples of the thienylunit with R₁ being part of a ring substituent structure are thefollowing:

wherein R₂ and R₃ are the same or different from each other, and areselected from the group consisting of:

(a) a hydrocarbon group (such as those described herein for theoptionally substituted indolocarbazole moieties),

(b) a heteroatom containing group (such as those described herein forthe optionally substituted indolocarbazole moieties),

(c) a halogen (such as those described herein for the optionallysubstituted indolocarbazole moieties), and

(d) a hydrogen.

The halogen for the optionally substituted indolocarbazole moieties isfluorine, bromine, chlorine, or iodine, or a mixture thereof.

The number of optionally substituted indolocarbazole moieties in theCompound is for example 2 to about 500, or 2 to about 100.

Illustrative Compounds are structures (1) through (6):

where n is an integer such as for example 2 to about 500, or 2 to about100.

Other exemplary embodiments of the Compound include for examplepoly(5,7-dialkylindolo[2,3-b]carbazole)s,poly(5,7-diarylindolo[2,3-b]carbazole)s,poly(5,8-dialkylindolo[2,3-c]carbazole)s, poly(5,8-diarylindolo[2,3-c]carbazole)s, poly(5,10-dialkylindolo[3,2-a]carbazole)s,poly(5,10-diarylindolo[3,2-a]carbazole)s,poly(5,12-dialkylindolo[3,2-c]carbazole)s,poly(5,12-diarylindolo[3,2-c]carbazole)s,poly(1,12-dialkylindolo[2,3-a]carbazole)s, andpoly(11,12-diarylindolo[2,3-a]carbazole)s.

In embodiments, a composition may be prepared which comprises two ormore Compounds in any suitable ratio by weight such as for example aratio ranging from about 1% (first Compound):99% (second Compound) toabout 99% (first Compound):1% (second Compound).

To be an efficient semiconductor for OTFTs, the optionally substitutedCompound in embodiments provides (i) proper molecular ordering conduciveto charge carrier transport; and (ii) sufficient stabilization to chargecarriers to enable efficient charge carrier injection. In embodiments,the Compound has one or more strategically placed substituentscomprising for example at least one long chain alkyl group (having forexample about 6 to about 18 carbon atoms in length) to promote molecularself-assembly, thus forming proper molecular ordering for charge carriertransport. In embodiments, the Compound also has one or morestrategically placed substituents such as for example aryl substituentsat the nitrogen positions to provide stabilization to injected chargecarriers. In embodiments, to provide stabilization to injected chargecarriers, the Compound is substituted with one or more substituentsindependently selected from the group consisting of a long chain alkylgroup (having for example about 6 to about 18 carbon atoms in length),an alkylphenyl (the alkyl of the alkylphenyl having for example 1 toabout 18 carbon atoms in length), a phenyl, a chloro, an alkoxy (havingfor example 1 to about 18 carbon atoms), and an amino (optionallysubstituted with one or two substituents such as for example ahydrocarbon group described herein), or a mixture thereof.

The Compound may be a p-type semiconductor or n-type semiconductor,depending very much on the nature of the substituents. Substituentswhich possess an electron donating property such as alkyl, alkoxy andaryl groups, when present in the Compound, render the Compound a p-typesemiconductor. On the other hand, substituents which are electronwithdrawing such as cyano, nitro, fluorinated alkyl, and fluorinatedaryl groups may transform the Compound into the n-type semiconductor.

In embodiments, the optionally substituted Compound has a band gap offor example greater than about 1.8 eV, greater than about 2.0 eV, orgreater than about 2.5 eV. The corresponding highest occupied molecularorbital (HOMO) energy level of the optionally substituted Compound isfor example lower than about 4.9 eV from vacuum, preferably lower thanabout 5.1 eV from vacuum. The optionally substituted Compound are inembodiments relatively stable against oxygen doping in air by virtue oftheir relatively low lying HOMOs.

In embodiments, the relatively low-lying HOMOs and large band gaps ofthe optionally substituted Compound generally provides many advantagesover other semiconductors. For example, in embodiments, the optionallysubstituted Compound generally has no or little absorbance in thevisible region of the spectrum, and is therefore expected to bephotochemically stable when exposed to light.

The Compound can be prepared by an appropriate coupling reaction of anoptionally substituted indolocarbazole (a single optionally substitutedindolocarbazole or a mixture of two or more different optionallysubstituted indolocarbazoles in any suitable ratios). The coupling agentor coupling agents may be for example an oxidizing agent. Anillustrative preparation of the Compound using an oxidative couplingreaction involves reacting a reaction mixture comprising a solvent (asingle solvent or a mixture of two or more different solvents in anysuitable ratios), an oxidizing agent (a single oxidizing agent or amixture of two or more different oxidizing agents in any suitableratio), and an optionally substituted indolocarbazole (a singleoptionally substituted indolocarbazole or a mixture of two or moredifferent optionally substituted indolocarbazoles in any suitableratios) at a suitable reaction temperature. By controlling the ratio ofcoupling agent to optionally substituted indolocarbazole under variousreaction conditions (e.g., reaction temperature, length of reactiontime, etc.), dimeric, oligomeric, or polymeric Compound can beselectively synthesized. In embodiments, the Compound can be furthersubstituted after the appropriate coupling reaction. For example, theillustrative Compound (8) can be obtained by further substituting theillustrative Compound (7) with two thienyl groups.

Any suitable optionally substituted indolocarbazole may be used to formthe Compound such as for example the optionally substitutedindolocarbazole selected from the group consisting of structures (A)through (G), or a mixture thereof and from the group consisting of thestructures (I) through (VIII), or a mixture thereof. The optionallysubstituted indolocarbazoles can be made with any suitable syntheticmethods. The optionally substituted indolocarbazoles and the synthesismethods are disclosed for example in U.S. Pat. Nos. 5,942,340;5,952,115; and 5,843,607, which are totally incorporated herein byreference.

Illustrative optionally substituted indolocarbazoles used to make theCompound are for example structures (I) through (VIII):

The reaction medium may be for example water or an organic reactionmedium such as for example chloroform, dichloromethane, chlorobenzene,dichlorobenzene, and the like, and mixtures thereof at any suitableratio. In embodiments, the reaction medium is a solvent for one or morecomponents of the reaction mixture.

Any suitable coupling agent may be used. Illustrative coupling agents,particularly oxidizing agents, are for example FeCl₃, FeBr₃, Fe₂(SO₄)₃,RuCl₃, MoCl₅, Na₂S₂O₈, K₂S₂O₈, K₂Cr₂O₇, KMnO₄, KBrO₃, KClO₃, and thelink, and mixtures thereof. The molar ratio of coupling agent tooptionally substituted indolocarbazole is for example from 1 to 20, orfrom 2 to 10. The reaction temperature may be for example from about−40° C. to about 200° C., or from about −20° C. to about 150° C., orfrom about 0° C. to about 100° C. The length of the reaction time canrange for example from about 1 hour to about 72 hours.

The desired Compound can be isolated for example by adding the reactionmixture to a non-solvent or a poor solvent of the Compound. Anon-solvent refers to any liquid in which the Compound is insoluble. Apoor solvent refers to any liquid in which the Compound has lowsolubility. Suitable non-solvents or poor solvents of the Compound mayinclude for example methanol, ethanol, propanol, acetone, and the like,and mixtures thereof. After isolation by precipitation from anon-solvent or a poor solvent, the Compound may be optionally treatedwith aqueous ammonia solution, a hydrazine solution, triethylamine, orother suitable base. The Compound can then be further purified byrepeated precipitation, extraction with one or more solvents, columnchromatography, sublimation, or other conventional techniques to removeresidual coupling agent and other undesired by-products.

The Compound can be optionally further purified by extraction via forexample Soxhlet extraction using one or more non-solvents or poorsolvents of the Compound to remove trace impurities and/or, in the caseof a polymeric compound, low molecular weight fractions.

Any suitable techniques may be used to form the semiconductor layercontaining the Compound. One such method is by vacuum evaporation at avacuum pressure of about 10⁻⁵ to 10⁻⁷ torr in a chamber containing asubstrate and a source vessel that holds the Compound in powdered form.Heat the vessel until the Compound sublimes onto the substrate. Theperformance of the films containing the Compound may depend on the rateof heating, the maximum source temperature and substrate temperatureduring the evaporation process. In embodiments, solution depositiontechniques may also be used to fabricate the semiconductor layercomprised of the Compound. Solution deposition techniques refer toliquid deposition processes such as spin coating, blade coating, rodcoating, screen printing, ink jet printing, stamping and the like.Specifically, the Compound can be dissolved in a suitable solvent of forexample tetrahydrofuran, dichloromethane, chlorobenzene, toluene, andxylene to form a solution at a concentration of about 0.1% to about 10%,particularly about 0.5% to. about 5% by weight, and then used insolution deposition. Ulustrative deposition by spin coating can becarried out at a spin speed of about 500 to about 3000 rpm, particularlyabout 1000 to about 2000 rpm for a period of time of about 5 to about100 seconds, particularly about 30 to about 60 seconds at roomtemperature or an elevated temperature to form a thin film on a suitablesubstrate such as silicon wafer, glass, or plastic film.

The semiconductor layer may be predominantly amorphous or predominantlycrystalline in nature, depending on the Compound and processingconditions. The semiconductor layer can be characterized by commoncharacterization techniques such as X-ray diffraction, atomic forcemicroscopy, optical microscopy, etc. For example, a predominantlyamorphous layer usually shows broad X-ray diffraction peaks, while apredominantly crystalline layer generally exhibits sharp X-raydiffraction peaks. The degree of crystallinity of a semiconductor layercan be calculated from the integrated area of diffraction peaks. Inembodiments, the phrase “predominately crystalline” indicates that thecrystallinity of the semiconductor layer is for example larger thanabout 50%, larger than about 80%, or larger than about 90%.

Depending on the nature of the Compound, a predominantly crystallinesemiconductor layer can be formed by a number of techniques. Forexample, a predominantly crystalline semiconductor layer can be formedby vacuum evaporation of the Compound onto a substrate holding at anelevated temperature of for example about 50° C. to about 120° C. Inanother technique, a predominantly crystalline semiconductor layer canbe achieved by solution coating followed by controlled solventevaporation and optionally post-deposition annealing at an elevatedtemperature of for example about 80° C. to about 250° C.

The exemplary use of Compound as a semiconductor in electronic devicesis illustrated herein using thin film transistors.

In FIG. 1, there is schematically illustrated an OTFT configuration 10comprised of a substrate 16, in contact therewith a metal contact 18(gate electrode) and a layer of a gate dielectric layer 14 on top ofwhich two metal contacts, source electrode 20 and drain electrode 22,are deposited. Over and between the metal contacts 20 and 22 is anorganic semiconductor layer 12 as illustrated herein.

FIG. 2 schematically illustrates another OTFT configuration 30 comprisedof a substrate 36, a gate electrode 38, a source electrode 40 and adrain electrode 42, a gate dielectric layer 34, and an organicsemiconductor layer 32.

FIG. 3 schematically illustrates a further OTFT configuration 50comprised of a heavily n-doped silicon wafer 56 which acts as both asubstrate and a gate electrode, a thermally grown silicon oxide gatedielectric layer 54, and an organic semiconductor layer 52, on top ofwhich are deposited a source electrode 60 and a drain electrode 62.

FIG. 4 schematically illustrates an additional OTFT configuration 70comprised of substrate 76, a gate electrode 78, a source electrode 80, adrain electrode 82, an organic semiconductor layer 72, and a gatedielectric layer 74.

The composition and formation of the semiconductor layer are describedherein.

The semiconductor layer has a thickness ranging for example from about10 nanometers to about 1 micrometer with a preferred thickness of fromabout 20 to about 200 nanometers. The OTFT devices contain asemiconductor channel with a width W and length L. The semiconductorchannel width may be, for example, from about 1 micrometers to about 5millimeters, with a specific channel width being about 5 micrometers toabout 1 millimeter. The semiconductor channel length may be, forexample, from about 1 micrometer to about 1 millimeter with a morespecific channel length being from about 5 micrometers to about 100micrometers.

The substrate may be composed of for instance silicon, glass plate,plastic film or sheet. For structurally flexible devices, a plasticsubstrate, such as for example polyester, polycarbonate, polyimidesheets and the like may be preferred. The thickness of the substrate maybe from about 10 micrometers to over about 10 millimeters with anexemplary thickness being from about 50 to about 100 micrometers,especially for a flexible plastic substrate and from about 1 to about 10millimeters for a rigid substrate such as glass plate or silicon wafer.

The gate electrode can be a thin metal film, a conducting polymer film,a conducting film made from conducting ink or paste, or the substrateitself can be the gate electrode, for example heavily doped silicon.Examples of gate electrode materials include but are not restricted toaluminum, gold, chromium, indium tin oxide, conducting polymers such aspolystyrene sulfonate-doped poly(3,4-ethylenedioxythiophene)(PSS-PEDOT), conducting ink/paste comprised of carbon black/graphite orcolloidal silver dispersion in polymer binders, such as ELECTRODAG™available from Acheson Colloids Company. The gate electrode layer can beprepared by vacuum evaporation, sputtering of metals or conductive metaloxides, coating from conducting polymer solutions or conducting inks byspin coating, casting or printing. The thickness of the gate electrodelayer ranges for example from about 10 to about 200 nanometers for metalfilms and in the range of about 1 to about 10 micrometers for polymerconductors.

The source and drain electrode layers can be fabricated from materialswhich provide a low resistance ohmic contact to the semiconductor layer.Typical materials suitable for use as source and drain electrodesinclude those of the gate electrode materials such as gold, nickel,aluminum, platinum, conducting polymers and conducting inks. Typicalthicknesses of source and drain electrodes are about, for example, fromabout 40 nanometers to about 10 micrometers with the more specificthickness being about 100 to about 400 nanometers.

The gate dielectric layer generally can be an inorganic material film oran organic polymer film. Illustrative examples of inorganic materialssuitable as the gate dielectric layer include silicon oxide, siliconnitride, aluminum oxide, barium titanate, barium zirconium titanate andthe like; illustrative examples of organic polymers for the gatedielectric layer include polyesters, polycarbonates, poly(vinyl phenol),polyimides, polystyrene, poly(methacrylate)s, poly(acrylate)s, epoxyresin and the like. The thickness of the gate dielectric layer is, forexample from about 10 nanometers to about 500 nanometers depending onthe dielectric constant of the dielectric material used. An exemplarythickness of the gate dielectric layer is from about 100 nanometers toabout 500 nanometers. The gate dielectric layer may have a conductivitythat is for example less than about 10⁻¹² S/cm.

The gate dielectric layer, the gate electrode, the semiconductor layer,the source electrode, and the drain electrode are formed in any sequencewith in embodiments the gate electrode and the semiconductor layer bothcontacting the gate dielectric layer, and the source electrode and thedrain electrode both contacting the semiconductor layer. The phrase “inany sequence” includes sequential and simultaneous formation. Forexample, the source electrode and the drain electrode can be formedsimultaneously or sequentially. The composition, fabrication, andoperation of field effect transistors are described in Bao et al., U.S.Pat. No. 6,107,117, the disclosure of which is totally incorporatedherein by reference.

For a p-channel OTFT, the source electrode is grounded and a biasvoltage of generally, for example, about 0 volt to about −80 volts isapplied to the drain electrode to collect the charge carrierstransported across the semiconductor channel when a voltage of generallyabout +20 volts to about −80 volts is applied to the gate electrode.

The semiconductor layer comprising the Compound in an OTFT devicegenerally exhibit a field-effect mobility of greater than for exampleabout 10⁻³ cm²/Vs (square centimeter per Volt per second), and an on/offratio of greater than for example about 10³. On/off ratio refers to theratio of the source-drain current when the transistor is on to thesource-drain current when the transistor is off.

The invention will now be described in detail with respect to specificexemplary embodiments thereof, it being understood that these examplesare intended to be illustrative only and the invention is not intendedto be limited to the materials, conditions, or process parametersrecited herein. All percentages and parts are by weight unless otherwiseindicated. As used herein, room temperature refers to a temperatureranging for example from about 20 to about 25° C.

EXAMPLE 1

(a) Synthesis of poly(5,11-dioctylindolo[3,2-b]carbazole):

A solution of 5,11-dioctylindolo[3,2-b]carbazole (0.481 g, 1.0 mmol) inchlorobenzene (10 mL) was added dropwise to a stirring mixture of FeCl₃(0.681 g, 4.2 mmol) and chlorobenzene (20 mL) in a 100 mL flask at 0° C.under an argon atmosphere. The solution became dark blue immediatelyupon addition. After stirring for 48 h at room temperature, the reactionmixture was poured into methanol (200 mL). The precipitated solidproduct was washed with water and methanol. After washing, the productwas suspended in dichloromethane (100 mL) with stirring while aqueousammonia solution (30%, 20 mL) was added. After stirring for 12 h, themixture was added to methanol. The solid product was collected andsubject to Soxhlet extraction, first with methanol for 24 h and thenwith heptane for another 24 h. The remaining solid product was isolatedby Soxhlet extraction with refluxing chlorobenzene. The resultingchlorobenzene solution was concentrated and then added to 100 mL ofstirring methanol to precipitate the product. The solid product wasdried under a reduced pressure overnight. Yield: 0.38 g.

(b) OTFT Fabrication and Evaluation.

A top-contact thin film transistor configuration as schematicallyillustrated, for example, in FIG. 3 was selected as our test devicestructure. The test device was built on an n-doped silicon wafer with athermally grown silicon oxide layer with a thickness of about 110nanometers thereon, and had a capacitance of about 30 nF/cm²(nanofarads/square centimeter), as measured with a capacitor meter. Thewafer functioned as the gate electrode while the silicon oxide layeracted as the gate dielectric. The silicon wafer was first cleaned withisopropanol, argon plasma, isopropanol and air dried, and then immersedin a 0.1 M solution of octyltrichlorosilane (OTS-8) in toluene at 60° C.for 20 min. Subsequently, the wafer was washed with toluene, isopropanoland air-dried. A solution of poly(5,11-dioctylindolo[3,2-b]carbazole)dissolved in dichlorobenzene (0.3 percent by weight) was first filteredthrough a 1.0 micrometer syringe filter, and then spin-coated on theOTS-8-treated silicon wafer at 1000 rpm for 120 seconds at roomtemperature. This resulted in the formation of a semiconductor layerwith a thickness of 20-50 nanometers on the silicon wafer, which wasthen dried in a vacuum oven at 80° C. for 5-10 h. Subsequently, goldsource and drain electrodes of about 50 nanometers in thickness weredeposited on top of the semiconductor layer by vacuum deposition througha shadow mask with various channel lengths and widths, thus creating aseries of transistors of various dimensions.

The evaluation of transistor performance was accomplished in a black box(that is, a closed box which excluded ambient light) at ambientconditions using a Keithley 4200 SCS semiconductor characterizationsystem. The carrier mobility, μ, was calculated from the data in thesaturated regime (gate voltage, V_(G)<source-drain voltage, V_(SD))according to equation (1)I _(SD) =C _(i)μ(W/2L)(V _(G) −V _(T))²   (1)where I_(SD) is the drain current at the saturated regime, W and L are,respectively, the semiconductor channel width and length, C_(i) is thecapacitance per unit area of the gate dielectric layer, and V_(G) andV_(T) are, respectively, the gate voltage and threshold voltage. V_(T)of the device was determined from the relationship between the squareroot of I_(SD) at the saturated regime and V_(G) of the device byextrapolating the measured data to I_(SD)=0.

The transfer and output characteristics of the devices showed that theCompound was a p-type semiconductor. Using transistors with a dimensionof W=5,000 μm and L=90 μm, the following average properties from atleast five transistors were obtained:

Mobility: 2.1-2.8×10⁻³ cm²/Vs

On/off ratio: 10⁴˜10⁵.

EXAMPLE 2

(a) Synthesis of poly(5,11-bis(4-octylphenyl)indolo[3,2-b]carbazole):

A solution of 5,11-bis(4-octylphenyl)indolo[3,2-b]carbazole (0.50 g,0.79 mmol) in chlorobenzene (10 mL) was added dropwise to a stirringmixture of FeCl₃ (0.58 g, 3.56 mmol) and chlorobenzene (10 mL) in a 100mL flask at room temperature under an argon atmosphere. The resultingmixture was stirred at 50° C. for 48 h and then poured into a stirringmethanol (200 mL). The precipitated solid product was washed with waterand methanol, and then suspended in dichloromethane (100 mL) whileaqueous ammonia solution (30%, 20 mL) was added. The resulting mixturewas stirred for 12 h and then added to 100 mL of stirring methanol. Thesolid product was collected and subjected to Soxhlet extraction, firstwith methanol for 24 h and then with heptane for 24 h. The remaininginsoluble solid product was isolated by Soxhlet extraction withrefluxing chlorobenzene. The resulting chlorobenzene solution wasconcentrated and then added to a stirring methanol (100 mL) toprecipitate the product. The solid product was dried under a reducedpressure overnight. Yield: 0.30 g.

(b) OTFT Device Fabrication and Evaluation.

OTFT devices using poly(5,11-bis(4-octylphenyl)indolo[3,2-b]carbazole)as the semiconductor were fabricated and characterized in accordancewith the procedures of Example 1. Using transistors with a dimension ofW=5,000 μm and L=90 μm, the following average properties from at leastfive transistors were obtained:

Mobility: 1.3-1.8×10⁻³ cm²/Vs

On/off ratio: 10⁴˜10⁵.

The mobility and current on/off ratio achieved by embodiments of thepresent thin film transistor devices are useful for various applicationsin electronics such as for example electronic paper.

1. A compound comprising a plurality of optionally substitutedindolocarbazole moieties which are the same or different from eachother.
 2. The compound of claim 1, wherein at least one of theindolocarbazole moieties has one or more nitrogen substitutions andoptionally has one or more peripheral substitutions.
 3. The compound ofclaim 1, wherein the number of the optionally substitutedindolocarbazole moieties ranges from 2 to about
 500. 4. The compound ofclaim 1, wherein the optional substituents of the optionally substitutedindolocarbazole moieties are independently selected from the groupconsisting of a hydrocarbon group, a heteroatom-containing group, and ahalogen, or a mixture thereof.
 5. The compound of claim 4, wherein theheteroatom-containing group is independently selected from the groupconsisting of fluoroalkyl, fluoroaryl, cyano, nitro, carbonyl,carboxylate, alkoxy, an optionally substituted thienyl, and anoptionally substituted amino, or a mixture thereof.
 6. A compoundcomprising a plurality of optionally substituted indolocarbazolemoieties, which are the same or different from each other, wherein theindolocarbazole moieties are independently selected from the structures(A), (B), (C), (D), (E), (F) and (G), or a mixture thereof:

wherein for each of the structures (A) through (G), each R isindependently selected from a group consisting of a hydrogen, ahydrocarbon group and a heteroatom-containing group, wherein each of thestructures (A) through (G) is optionally peripherally substituted. 7.The compound of claim 6, wherein for each of the structures (A) through(G), each R is independently selected from a group consisting of ahydrocarbon group and a heteroatom-containing group, wherein each of thestructures (A) through (G) is optionally peripherally substituted. 8.The compound of claim 6, wherein the number of the optionallysubstituted indolocarbazole moieties ranges from 2 to about
 500. 9. Thecompound of claim 6, wherein the compound is selected from the groupconsisting of (1) through (10), or a mixture thereof:

wherein n is an integer.
 10. The compound of claim 6, wherein thecompound is a molecular compound.
 11. The compound of claim 6, whereinthe compound is an oligomer.
 12. The compound of claim 6, wherein thecompound is a polymer.
 13. An electronic device comprising: a substrate;an electrically conductive layer or a dielectric layer, or both theelectrically conductive layer and the dielectric layer; and asemiconductor layer comprising a compound comprising a plurality ofoptionally substituted indolocarbazole moieties which are the same ordifferent from each other.
 14. A thin film transistor comprising: (a) agate dielectric layer; (b) a gate electrode; (c) a semiconductor layer;(d) a source electrode; and (e) a drain electrode, wherein the gatedielectric layer, the gate electrode, the semiconductor layer, thesource electrode, and the drain electrode are in any sequence as long asthe gate electrode and the semiconductor layer both contact the gatedielectric layer, and the source electrode and the drain electrode bothcontact the semiconductor layer, and wherein the semiconductor layerincludes a compound comprising a plurality of optionally substitutedindolocarbazole moieties, which are the same or different from eachother, wherein the indolocarbazole moieties are independently selectedfrom the structures (A), (B), (C), (D), (E), (F) and (G), or a mixturethereof:

wherein for each of the structures (A) through (G), each R isindependently selected from a group consisting of a hydrogen, ahydrocarbon group and a heteroatom-containing group, wherein each of thestructures (A) through (G) is optionally peripherally substituted. 15.The transistor of claim 14, wherein the compound is selected from thegroup consisting of (1) through (10), or a mixture thereof:

wherein n is an integer.
 16. The transistor of claim 14, wherein thecompound has a band gap of greater than about 1.8 eV.
 17. The transistorof claim 14, wherein the compound has a highest occupied molecularorbital energy level lower than about 4.9 eV from vacuum.
 18. Thetransistor of claim 14, wherein the compound is substituted with atleast one long chain alkyl to promote molecular self-assembly.
 19. Thetransistor of claim 14, wherein the compound is substituted with one ormore substituents independently selected from the group consisting of along chain alkyl group, an alkylphenyl, a phenyl, a chloro, an alkoxy,an optionally substituted thienyl, and an optionally substituted amino,or a mixture thereof.
 20. The transistor of claim 14, wherein thesemiconductor layer is predominately crystalline.